Treatment of textiles and composition useful therefor



Patented reazs, 1944,

TREATDIENT OF rnxmas AND courosr- TION USEFUL THEREFOR Joseph Edward Smith, Wilmington, net. aasignor to E. L du Pont de Nemours & Company, Wilmington, Dcl., a corporation of Delaware No Drawing. Application August 3,1940, Serial No. 351.088

2 Claims. (01260-8) This invention relates to aqueous dispersions or resins substantive to animal fibers, nylon and cellulosic fibers and more particularly to aqueous dispersions of resins substantive to animal fibers, nylon and cellulosic fibers prepared using a mixture comprising a polyvinyl ester containing hydroiwl groups, a water soluble salt of deacetylated chitin and cationic surface active compound as emulsifier.

This invention relates further to a process of treating textile fabrics and knit good with resin dispersions and more particularly to a process of treating textile fabrics and knit goods by a proces of exhausting the dispersed phase from a dilute suspension of a resin.

This invention relates further to new textile articles, and more particularly to new textile articles having a starch-like finish in the absence of starch which is substantially unaffected by laundering. This invention relates further to textile articles having a delustered appearance which is substantially unaffected by laundering. This invention relates further to textile articles, the threads of which have a resistance to both slipping and snagging. substantially unaffected by laundering.

This invention has as an object the preparation of aqueous dispersions of resins substantive to animal fibers,'nylon and cellulosic fibers. A further object is the treatment of textile fabrics and knit goods with resin dispersions by a process of exhausting the dispersed phase from a dilute suspension onto the goods A still further object is the production of new textile articles having a starch-likefinish in the absence of starch which is substantially unaffected by laundering. Another object is the preparation of textile articles having a non-chalky delustered appearance which is substantially unafiected by laundering. Another object of this invention is the production of textile articles the threads of which have a resistance to both slipping and snagging substantially unaffected by laundering. Other objects will appear hereinafter.

These objects are accomplished by the following procedure. A small amount of benzoyl peroxide is dissolved in one or more polymerizable conjugated compounds which may, in addition, contain in solution a natural or synthetic resin soluble in the polymerizable conjugated compound. The solution of the resin components is agitated vigorously with a solution in water of a partially saponified polyvinyl acetate and a water soluble salt of deacetylated chitin. The aqueous solution may contain in addition a multivalent metal or heavy metal salt, an acid, and a cationic surface active agent. The emulsion is heated to produce polymerization of the ester monomer. A stable dispersion of the resin is formed. The dispersed resin is applied to a fabric by an impregnation step or by a process of exhausting from a dilute suspension in water. Finishes obtained by applying the dispersions to animal fibers, cellusosic and modified cellulosic fibers and to nylon are quite durable to laundering.

The preparation of aqueous dispersions of olymerized conjugated compounds and of mixed polymers of polymerizable conjugated compounds with resins soluble in their monomers is described in my copending applications, Serial Nos. 351,082, 351,083, 351,084, 351,085, 351,080, and 351,087 filed on this same day. The dispersed particles in these aqueous dispersions have varying degrees of substantivity for textile fibers depending on the presence of metal salts and cationic surface active agents in the dispersions. While the starch-like finishes obtained in applying these dispersions to textiles are durable to laundering as compared with similar finishes obtained using starches, dextrines, and gums, they nevertheless are affected by a laundering process so that an appreciable decrease in the effective hand is very often noticed after a severe laundering. The finishes describedin the present invention produce a starch-like sizing effect markedly improved in durability to laundering. In addition the dispersions formed in this invention have the valuable property of being substantive to animal fibers, nylon and cellulosic materials In carrying out the invention, an aqueous solution containing a partially saponified polyvinyl acetate and an acetate of deacetylated chitin is agitated vigorously with one or more liquid monomeric polymerizable conjugated compounds containing a small amount of benzoyl peroxide. The'monomers may contain in addition substantial proportions of soluble natural and synthetic resins and plasticizers. A stable emulsion is obtained. The emulsion is heated for several hours at a temperature above and preferably above C. to effect polymerization. A stable resin dispersion is obtained.

As a modification of this procedure the aqueous solution containing the emulsifying agent may contain in addition the water-soluble salt of a heavy ormultivalent metal, as aluminum acetate. Dispersions containing aluminum acetate have a greater afilnity for animal fibers than those contalning no metal salt.

The aqueous solution may contain in addition a cationic surface active agent. Dispersions containing the cationic surface active agent have excellent a-fiinity, when applied from dilute suspension, not only for animal fibers and nylon, but also for cellulosic materials.

The partially saponified polyvinyl acetate used in dispersions containing substantial proportions of methacrylates should have a saponification number in the range -128 and produce a viscosity of 20 to 40 centipoises for a 4% aqueous solution at 20" C. p

The resin dispersions described herein produce a starch-like efiect when applied from aqueous dispersion as a sizing'agent for textiles. The sizing eii'ect obtained is considerably faster to laundering than is obtained with compositions described in my copending applications, Serial Nos. 351,082, 351,083, 351,084, 351,085, 351,086, and 351,087, filed on this same day, and in many instances appearsunafiected by a wash in an alkaline soap solution in a laundry wheel at the boil.

The improved fastness to laundering is believed to be caused by increased adhesion of the compositions described in this invention to textile materials. Films prepared by drying these compositions on a surface of regenerated cellulose sheeting adhere strongly to the sheet and cannot be scraped 01!. Similar films prepared with compositions described in my copending applications, Serial Nos. 351,082 and 351,085, filed on this same day, adhere much less tenaciously to regenerated cellulose sheeting.

The dispersed resin is alsosubstantive to animal fibers, nylon and cellulosic fibers when applied in a similar manner to dispersions prepared as described in my copending applications, Serial Nos. 351,083, 351,084, 351,086, and 351,087, filed on this same day. The resin dispersions prepared by the methods described herein are positively charged and can be applied to textiles in combination with other positively charged emulsions or dispersions and with cationic surface active agents.

The following examples are illustrative of the invention but are not intended as limiting it in any way. Parts are given by weight except where it may be otherwise indicated.

Exam 1 Twenty parts of methyl methacrylate monomer containing 0.2 part of benzoyl peroxide was mixed with high-speed agitation with 80 parts of an aqueous solution containing 2 parts of a partially saponified polyvinyl acetate (saponiflcation number 108; viscosity in 4% aqueous solution at 20 C., 20 c. p.), one part of an acetate of deacetylated chitin (viscosity for a 5% aqueous solution at 20 C., 30-40 poises) and 0.3 part of acetic acid. A stable emulsion was obtained. The emulsion was aged for 4 hours at 65 C. to obtain a stable dispersion of a resinous polymer.

Exams: 2

0.3 gram of the product from Example 1 was diluted with 199.7 grams of water to obtain a dilute dispersion of pH 6.5. A l0-gram silk stocking was entered in the bath and agitated for 15 minutes at 100 F. More than 75% of the dispersion was absorbed by the silk. The stocking was hydro-extracted and boarded on an electrically-heated form. An excellently delustered stocking was obtained. The delustered eilect was durable to short washings at 110 F.

EXAHPLI 3 Exmrnz .4

The monomer of n-butyl methacrylate was substituted for the methyl methacrylate monomer in Example 1. A stable dispersion of a resinous polymer was obtained.

Exsuru: 5

Ten parts of the product from Example 4 were dispersed with parts of water. The bath was used to impregnate a strip of bleached cotton muslin to obtain a increase in weight. The fabric was dried on a mangle at about 260 F. A crisp starch-like finish was obtained.

A .portion of the treated fabric was washed on a wash wheel for 40 minutes at the boil in an aqueous solution containing 0.25% soap and 0.1% soda ash. The hand of the fabric was changed only slightly.

ExAuPLr 6 Iso-butyl methacrylate was substituted for the methyl methacrylate in Example 1. A stable dispersion of a resinous polymer was obtained.

The product was applied to bleached cotton muslin as in Example 5 to obtain a similar full, crisp, starch-like finish. The hand of the treated fabric was affected only slightly by the wash test of Example 5.

EXAMPLE 7 The n-butyl methacrylate of Example 4 was substituted by 18 parts of n-butyl methacrylate and 2 parts of di-(butoxy ethyl) phthalate. A stable dispersion of a resinous polymer was obtained. The product was applied to bleached cotton muslin as in Example 5 to obtain a full, starch-like finish. The hand of the treated fabric was affected only slightly by the wash test of Example 5.

EXAMPLE 8 The n-butyl methacrylate of Example 4 was substituted by 18 parts of n-butyl methacrylate and 2 parts of di-(methylcyclohexyl) adipate. The results obtained were similar to those of Example 7.

EXAMPLE 9 EXAMPLE 10 Twenty parts of vinyl acetate monomer were substituted for the methyl methacrylate in Exampie 1. A stable dispersion of a resin polymer was obtained on aging for 6 hours at 65 C.

The product was applied to bleached cotton muslin as in Example 5 to obtain a full, stiff, crisp, starch-like finish. The hand of the treat- Water amp edi'abriswal aflectedonlynoticeablybyawash test as in Example 5.

Exmt 1l Twenty parts of methyl methacrylate monomer containing 0.2 part of benzoyl peroxide were agitated by means of a high-speed mixer with 74.8 parts of an aqueous solution containing 2 parts of a partially saponified polyvinyl acetate (saponification number 108, viscosity for a 4% aqueous solution at 20 C., 20 c. p.), 0.02 parts of technical dodecyl diethylcyclohexylamine sulfate, 1 part of an acetate of deacetylated chitin and 0.7 parts acetic acid. While continuing the agitation 4.5 parts of a 32% basic aluminum acetate solution and 0.7 part of acetic acid were added. A stable emulsion was obtained. The emulsion was aged for 4 hours at 65 C. to obtain 'a stable dispersion of a resin polymer.

The dispersion when applied to a sill: stocking as in Example 2 exhausted almost completely from thebath onto the stocking.

Exmna 12 0.5 gram of the product from-Example 1 and 0.3 gram of Composition A were diluted with 199.2 grams of water. Composition A is Per cent Refined paraflln wax 16.7 Acetate of deacetylated chitin 1.3 Basic aluminum acetate 3.0 Acetic acid 0.5

Technical dodecyl diethylcyclohexylamine sulfate 0.09 78.41

A -gram silk stocking was entered in the bath and agitated for 10 minutes at 80 F., 5 minutes at 100 F. The dispersion was completely exhausted from the bath by the stocking. The stocking was hydro-extracted and boarded on an electrically-heated form. The finished stocking was highly delustered and water repellent.

Exam: 13'

Four parts of the product from Example 4 and 4 parts of Composition A were diluted with 92 parts of water and applied to bleached cotton muslin by an impregnation method to obtain 100% increase in weight. The fabric was dried on a mangle heated to about 260 F. The fabric was well filled and had excellent body. The water-repellency was excellent. The water-repellent finish was more durable to washing than could be obtained'with Composition A alone.

Exmn: 14

Eight parts of a glyceryl ester of abietlc acid and 0.2 part of benzoyl peroxide were dissolved in 12 parts of methyl methacrylate monomer and agitated by means of a high-speed mixer with 74.8 parts of an aqueous solution containing 2 parts of a partially saponified polyvinyl acetate (saponification number 108; viscosity for a 4% aqueous solution at C., 20 c. p.), 0.02 part oi I technical dodecyl diethylcyclohexylamine sulfate,

one part of an acetate of deacetylated chitin, 0.6 part of stearyl trimethyl ammonium bromide and 0.7 part of acetic acid. While continuing the agitation 4.5 parts of a 32% basic aluminum acetate solution and 0.7 part of acetic acid were added. A stable emulsion was obtained. The emulsion was aged 4 hours at 65 C. to. obtain a stable dispersion of .a resin polymer.

minutes.

. minutes.

persed phase was exhausted to the extent of from the bath as judged by a turbidity method. The resin imparted a full. well-delustered finish to the stocking. The finish was of excellent resistance to laundering in an 0.5% soap solution at 105 F.

(b) One gram of the product from Example 14 was dispersed in 200 cc. of water contained in a pint Mason jar. A 10-gram nylon stocking was entered in the bath at 80 F. and agitated five The temperature was raised to 120 F. and agitation continued 25'minutes. The dispersed phase was exhausted to the extent of 80% from the bath as Judged by a turbidity method. The finish imparted was full and well delustered. The stocking was of much improved snag resistance compared with an untreated stocking. The finish was of excellent resistance to laundering in an 0.5% soap solution at 105 F.

(c) 0.5 gram of the product from Example 14 were dispersed in 200 cc. of water contained in a pint Mason jar. A IO-gram strip of black dyed viscose process rayon knit fabric was entered in the bath at F. and agitated 30 minutes. The dispersed phase was exhausted to the extent of 75% from the bath as judged by a turbidity method. The finish imparted was full, crisp and well delustered. The finish was of excellent resistance to laundering in a 0.5% soap solution at F.

(d) The product from Example 14 was applied to cellulose acetate rayon piece-goods as in Ha. A full, crisp, well delustered finish was obtained.

Exmts 16 0.6 part of cetyl pyridinium bromide was substituted for the stearyl trimethyl ammonium bromide in Example 14. A similar product was obtained as shownby application tests by the methods of Example 15.

- Exmu: 17

Exmrrs 18 0.6 part of the reaction product of alpha bromstearic acid and trimethylamine (U. 8. Patent 2,129,264) was substituted for the stearyl trimethyl ammonium bromide of Example 14. A similar product was obtained as shown by application tests carried out as in Example 15.

Equal parts of aluminum formate and formic acid were substituted for the aluminum acetate and acetic acid in Example 11. A similar product was obtained. I

' Exams: 20

An equal amount of barium chloride was substituted for the aluminum acetate in Example 11. A similar product was obtained.

A IO-gram silk stocking was Emu: 21

The glyceryl ester of abietic acid in Example 14 was replaced by an equal weight of a rosin modified alkyd resin. A stable resin dispersion having excellent affinity for silk, nylon, cellulose acetate rayon and viscose process rayon was obtained. The'finishes obtained on application by the methods of Example 15 were similar. to those described in that example.

Exams: 22

A modified tertiary butyl phenol-formaldelwde resin was substituted for the glyceryl ester of abietic acid in Example 14. A stable resin dispersion having excellent amnity for silk, nylon, cellulose acetate rayon and viscose process rayon was obtained. The finishes obtained on application by the methods of Example 15 were similar to those described in that example.

Exmrrs 23 y A cumarone-indene resin was substituted for the glyceryl ester of abietic acid and vinyl acetate was substituted for the methyl methacrylate in Example 14. A stable resin dispersion was obtained. The dispersion had excellent affinity for silk, nylon, cellulose acetate rayon and viscose process rayon when applied by the methods of Example 15. The finishes were characterized by fullness and leatheriness. Excellent snag resistance was obtained on the silk and nylon hosiery. The finishes were of excellent fastness to washing.

Exurrr: 24

A batch of 100 lbs. of dyed silk stockln8s was treated with lbs. of the product from Example 1 and 3 lbs. of Composition A (see Example 12) in a 100-lb. Smith-Drum rotary type machine. The dispersions, diluted with water, were added to the loaded machine at 75 F. and the bath agitated for minutes. The temperature of the bath was raised to 100 F. and agitation continued 5 minutes. The dispersed phase was almost completely removed from the bath by the stockings. The final pH of the bath was 6.2. The stockings were hydro-extracted, then boarded and dried on steam-heated forms. The stockings had a full, soft hand, were water repellent and markedly delustered. The delustered effect on the stockings was quite resistant to removal by ten short washes in 0.5% soap solution at 105 F.

The methacrylate derivatives and the vinyl acetate disclosed in the preceding examples can bereplaced by polymerizable conjugated compounds, particularly vinyl derivatives including chloroprene, butadiene, vinyl chloride, methyl vinyl ketone, styrene, acrylonitriles, methacrylonitrlles, acrylamides, methacrylamides, and acrylates. The polymerization must be carried out under pressure when the conjugated compounds are gases at atmospheric pressure. The glyceryl ester of abietic acid can be replaced by other resins soluble in the monomers, as rosin derivatives in general, phenol-formaldehyde and modified phenol-formaldehyde resins, alhd and modified alkyd resins and cumarone-indene resins. Suitable plasticizers are discussed by Strain, Kennelly and Dittmar, Ind. Eng. Chem. 31,- 382, (1939).

For other suitable water-soluble salts of deaoetylated chitin besides the acetate, reference is made to'Patterson and Peterson U. 8. Patent 2,047,220.

assaoas The partially saponified polyvinyl acetate used for methacrylate dispersions should have a saponiflcation number in the range 5-130 and a 4% I aqueous solution should have a viscosity of 20 to 40 c.p. at 20 C. The. acetate of deacetylated chitin preferably gives a viscosity of 30-40 poises for a 5% solution in dilute acetic acid; however, material which produces solutions of a much wider viscosity range is satisfactory.

Other substantially non-polar high molecular weight water-soluble protective colloids may be used in place of partiallysaponified polyvinyl acetate. In place of partially saponified polyvinyl acetate there may be used cellulose derivatives such as water-soluble methyl cellulose, the etcthylene oxide reaction product of oleyl alcohol, e

Products described in this invention are useful for producing starch-like finishes having excellent durability to laundering on textile fabrics. Products described in this invention are useful as sizing agents for knit goods as well as fabrics and can be applied if desired by a process of exhaustion from a dilute suspension. Products described in this invention are useful, not only for producing starch-like finishes, but also as delusterants, snag-proofing and slip-proofing agents.

The invention has as an advantage the preparation of compositions which produce starchlike finishes which have excellent durability to laundering on textiles, and are markedly improved in fastness compared with similar compositions which do not contain an acetate of deacetylated chitin.

An added advantage is the preparation of excellent non-chalky delusterants for textile fabrics and knit goods using methyl methacrylate as the monomeric derivative.

Another advantage is the preparation of laundry-fast finishes for textiles which can be applied by a process of exhaustion from a dilute bath to animal fibers, nylon and cellulosic fibers.

Still another advantage is the preparation of compositions which produce increased resistance to snagging and slipping onrayon and nylon fabrics and knit goods.

agent a partially saponified polyvinyl acetate having a saponification number of from 5 to 128 and a viscosity in a 4% aqueous solution at 20 C. of from 20 to 40 centipoises, the amount of the acetate of deacetylated chitin being sufllcient to impart to said fiber-finishing composition the property of rendering to textiles a non-chalky, delusteredfinish.

2. A non-chalky, delustered textile fiber obtained by applying to said textile fiber the composition of claim 1.

JOSEPH EDWARD SMITH. 

